Challenges associated with quantification of selected urinary biomarkers of exposure to tobacco products.

Tobacco use, of which cigarette smoking is the most common, is a global health concern and is directly linked to over 7 million premature deaths annually. Measurement of the levels of tobacco-related biomarkers in biological matrices reflects human exposure to the chemicals in tobacco products. Nicotine, nicotine metabolites, anatabine, and anabasine are specific to tobacco and nicotine containing products. However, as nicotine and its metabolites are ubiquitous in the environment, background contamination during sample preparation can occur, making the quantification of target analytes challenging. The main purpose of the present study was to examine quality control measures needed in the determination of urinary nicotine, nicotine metabolites, anatabine, and anabasine. Urine samples (n = 75) and NIST standard reference materials SRM 3671 and SRM 3672 were analysed. A one-step extraction procedure using cold acetone was used in this study, which involved no additional clean up. The blank matrices investigated included synthetic urine prepared with HPLC-grade water, synthetic urine prepared with Milli-Q water, and bovine urine. By adopting strategies for minimizing the background levels, very low detection limits for all the target analytes ranging from 0.025 ng/mL for 3-hydroxycotinine to 0.634 ng/mL for nicotine, were achieved. Recoveries ranged between 67% and 118% with RSD values below 20%. Intra-day and inter-day precisions were in the range of 1.1-11.7% and 4.8-25.2%, respectively. The levels of all target analytes were higher in daily smokers than in non-smokers, with the largest difference observed for 3-hydroxycotinine. No difference was observed in the levels of target analytes between individuals who were former smokers, who never smoked or who were exposed to environmental tobacco smoke (ETS), except for total nicotine equivalents (TNE), which was significantly higher in non-smokers exposed to environmental tobacco smoke compared with study participants who never smoked. The results obtained from SRM 3671 and SRM 3672 could inform a potential certification of additional biomarkers of exposure to tobacco products in those standard reference materials.

A review of the analysis of biomarkers of exposure to tobacco and vaping products.

Quantification of exposure to different chemicals from both combustible cigarettes and vaping products is important in providing information on the potential health risks of these products. To assess the exposure to tobacco products, biomarkers of exposure (BOEs) are measured in a variety of biological matrices. In this review paper, current knowledge on analytical methods applied to the analysis of biomarkers of exposure to tobacco products is discussed. Numerous sample preparation techniques are available for the extraction and sample clean up for the analysis of BOEs to tobacco and nicotine delivery products. Many tobacco products-related exposure biomarkers have been analyzed using different instrumental techniques, the most common techniques being gas and liquid chromatography coupled with mass spectrometry (GC-MS, GC-MS/MS and LC-MS/MS). To assess exposure to emerging tobacco products and study exposure in dual tobacco users, the list of biomarkers analyzed in urine samples has been expanded. Therefore, the current state of the literature can be used in preparing a preferred list of biomarkers based on the aim of each study. The information summarized in this review is expected to be a handy tool for researchers involved in studying exposures to tobacco products, as well as in risk assessment of biomarkers of exposure to vaping products.

A theoretical investigation on the kinetics and mechanism of the reaction of amidogen with hydroxyl radical.

The kinetics and mechanism of the reaction between amidogen radical and hydroxyl radical have been theoretically investigated on the lowest singlet and triplet surfaces. The singlet surface consists of two long-lived chemically activated NH(2)OH* and NH(3)O* intermediates with 10 different channels. A hydrogen abstraction channel on the triplet surface proceeds through van der Waals complex in both reactant side and product side to produce NH(3) + O((3)P). The effect of multiple reflections of the van der Waals complexes on the rate constant is investigated. Multichannel RRKM-TST calculations have been carried out to calculate the individual rate constants for the formation of those products that proceed through activated adducts on the singlet surface. The rate constants for direct hydrogen abstraction reactions were calculated by using direct-dynamics canonical variational transition-state theory with small curvature approximation for tunneling.

Water-based oxygen-sensor films.

The luminescent cyclometalated iridium complex [Ir(fppy)(2)(t-Bu-iCN)(2)]CF(3)SO(3), 1 (fppy = 4-(2-pyridyl)benzaldehyde, and t-Bu-iCN = tert-butyl isocyanide), was synthesized and characterized by X-ray crystallography and (1)H NMR, absorption, and emission spectroscopies. Complex 1 was quantitatively bound to the water-soluble amine-functionalized polymer Silamine D208-EDA by reductive amination, to produce 2. The quantum yield of emission and excited state lifetime of 2 (varphi(em) = 0.23 and tau = 20.6 mus) are comparable to that of the model complex [Ir(tpy)(2)(t-Bu-iCN)(2)]CF(3)SO(3), 3 (tpy = 2-(p- tolyl) pyridine) with varphi(em) = 0.28 and tau = 35.6 mus. Aqueous blends of 2 with Silamine and colloidal microcrystalline cellulose (MC) were used to prepare oxygen-sensor films. Oxygen sensitivities of these films were determined as a function of Silamine:MC ratio and obeyed Stern-Volmer kinetics. The optimum oxygen-sensor film composition was 2 in 1:1 Silamine:MC, which had an oxygen sensitivity of 0.502 over an atmospheric pressure range of 0.007-45 psi. Temperature sensitivity (percentage loss of intensity per degrees C) of this film was determined to be -1.1 and -1.4% degrees C(-1) at vacuum and 1 bar atmospheric pressure, respectively. These results were compared to those of films incorporating dispersions of 1 and 3. Luminescence microscopy of 9:1, 1:1, and 1:5 Silamine:MC films of 2 show that the charged iridium complex in 2 associates with the surface of MC and lifetime measurements of these films show an increase in lifetime with increasing MC fraction. The optimum quenching sensitivity observed for the 1:1 Silamine:MC film suggests that the diffusion of oxygen must decrease with increasing fraction of MC and thereby decrease oxygen sensitivity. These novel materials offer an environmentally friendly alternative to the preparation of oxygen-sensor films.